Sustainable ABA Triblock Methacrylate Copolymers Incorporating both High and Low Tg Terpene-Derived Monomers

Rachel L. Atkinson; Matthew Elsmore; Sean Smith; Morgan Reynolds-Green; Paul D. Topham; Daniel T.W. Toolan; Matthew J. Derry; Olivia Monaghan; Vincenzo Taresco; Derek J. Irvine; Robert A. Stockman; Davide S.A. De Focatiis; Steven M. Howdle

doi:10.1016/j.eurpolymj.2022.111567

Sustainable ABA Triblock Methacrylate Copolymers Incorporating both High and Low Tg Terpene-Derived Monomers

Rachel L. Atkinson, Matthew Elsmore, Sean Smith, Morgan Reynolds-Green, Paul D. Topham, Daniel T.W. Toolan, Matthew J. Derry, Olivia Monaghan, Vincenzo Taresco, Derek J. Irvine, Robert A. Stockman^*, Davide S.A. De Focatiis^*, Steven M. Howdle^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

We report the synthesis of novel terpene-based monomers: nopinyl acrylate and methacrylate, from naturally abundant β-pinene. A very high Tg value was observed for poly(nopinyl methacrylate) when synthesised by free radical polymerisation, and well-defined polymers have been produced via RAFT polymerisation. This exciting new high Tg material shows promise as a hard block in thermoplastic elastomers. ABA triblock copolymers have been synthesised which also incorporate a low Tg renewable soft block, poly(tetrahydrogeraniol methacrylate), using a divergent, difunctional RAFT polymerisation method. Initial phase separation behaviour and adhesive properties have been investigated to highlight the potential of these copolymer materials as renewably sourced thermoplastic elastomers.

Original language	English
Article number	111567
Number of pages	10
Journal	European Polymer Journal
Volume	179
Early online date	9 Sept 2022
DOIs	https://doi.org/10.1016/j.eurpolymj.2022.111567
Publication status	Published - 5 Oct 2022

Bibliographical note

© 2022 Published by Elsevier Ltd.

Funding Information:
This work was carried out with the support of Diamond Light Source, beamline I22 (proposal SM23501). Professor Nick J. Terrill and Dr Andrew J. Smith are thanked for help and advice during SAXS data collection.

Funding Information:
This work was supported by the Engineering and Physical Sciences Research Council [grant numbers EP/N019784/1,]; the School of Chemistry, University of Nottingham. We thank Mark Guyler (University of Nottingham) for his technical support with all the laboratory equipment. We are indebted to Shazad Aslam and Kevin Butler for their technical input to analysis by NMR. This work was carried out with the support of Diamond Light Source, beamline I22 (proposal SM23501). Professor Nick J. Terrill and Dr Andrew J. Smith are thanked for help and advice during SAXS data collection.

Funding Information:
This work was supported by the Engineering and Physical Sciences Research Council [grant numbers EP/N019784/1,]; the School of Chemistry, University of Nottingham. We thank Mark Guyler (University of Nottingham) for his technical support with all the laboratory equipment. We are indebted to Shazad Aslam and Kevin Butler for their technical input to analysis by NMR.

Publisher Copyright:
© 2022

Keywords

Terpenes
Nopinyl
ABA Triblocks
Biorenewable monomers
RAFT

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10.1016/j.eurpolymj.2022.111567

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Atkinson, R. L., Elsmore, M., Smith, S., Reynolds-Green, M., Topham, P. D., Toolan, D. T. W., Derry, M. J., Monaghan, O., Taresco, V., Irvine, D. J., Stockman, R. A., De Focatiis, D. S. A., & Howdle, S. M. (2022). Sustainable ABA Triblock Methacrylate Copolymers Incorporating both High and Low Tg Terpene-Derived Monomers. European Polymer Journal, 179, Article 111567. https://doi.org/10.1016/j.eurpolymj.2022.111567

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title = "Sustainable ABA Triblock Methacrylate Copolymers Incorporating both High and Low Tg Terpene-Derived Monomers",

abstract = "We report the synthesis of novel terpene-based monomers: nopinyl acrylate and methacrylate, from naturally abundant β-pinene. A very high Tg value was observed for poly(nopinyl methacrylate) when synthesised by free radical polymerisation, and well-defined polymers have been produced via RAFT polymerisation. This exciting new high Tg material shows promise as a hard block in thermoplastic elastomers. ABA triblock copolymers have been synthesised which also incorporate a low Tg renewable soft block, poly(tetrahydrogeraniol methacrylate), using a divergent, difunctional RAFT polymerisation method. Initial phase separation behaviour and adhesive properties have been investigated to highlight the potential of these copolymer materials as renewably sourced thermoplastic elastomers.",

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author = "Atkinson, {Rachel L.} and Matthew Elsmore and Sean Smith and Morgan Reynolds-Green and Topham, {Paul D.} and Toolan, {Daniel T.W.} and Derry, {Matthew J.} and Olivia Monaghan and Vincenzo Taresco and Irvine, {Derek J.} and Stockman, {Robert A.} and {De Focatiis}, {Davide S.A.} and Howdle, {Steven M.}",

note = "{\textcopyright} 2022 Published by Elsevier Ltd. Funding Information: This work was carried out with the support of Diamond Light Source, beamline I22 (proposal SM23501). Professor Nick J. Terrill and Dr Andrew J. Smith are thanked for help and advice during SAXS data collection. Funding Information: This work was supported by the Engineering and Physical Sciences Research Council [grant numbers EP/N019784/1,]; the School of Chemistry, University of Nottingham. We thank Mark Guyler (University of Nottingham) for his technical support with all the laboratory equipment. We are indebted to Shazad Aslam and Kevin Butler for their technical input to analysis by NMR. This work was carried out with the support of Diamond Light Source, beamline I22 (proposal SM23501). Professor Nick J. Terrill and Dr Andrew J. Smith are thanked for help and advice during SAXS data collection. Funding Information: This work was supported by the Engineering and Physical Sciences Research Council [grant numbers EP/N019784/1,]; the School of Chemistry, University of Nottingham. We thank Mark Guyler (University of Nottingham) for his technical support with all the laboratory equipment. We are indebted to Shazad Aslam and Kevin Butler for their technical input to analysis by NMR. Publisher Copyright: {\textcopyright} 2022",

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Atkinson, RL, Elsmore, M, Smith, S, Reynolds-Green, M, Topham, PD, Toolan, DTW, Derry, MJ, Monaghan, O, Taresco, V, Irvine, DJ, Stockman, RA, De Focatiis, DSA & Howdle, SM 2022, 'Sustainable ABA Triblock Methacrylate Copolymers Incorporating both High and Low Tg Terpene-Derived Monomers', European Polymer Journal, vol. 179, 111567. https://doi.org/10.1016/j.eurpolymj.2022.111567

TY - JOUR

T1 - Sustainable ABA Triblock Methacrylate Copolymers Incorporating both High and Low Tg Terpene-Derived Monomers

AU - Atkinson, Rachel L.

AU - Elsmore, Matthew

AU - Smith, Sean

AU - Reynolds-Green, Morgan

AU - Topham, Paul D.

AU - Toolan, Daniel T.W.

AU - Derry, Matthew J.

AU - Monaghan, Olivia

AU - Taresco, Vincenzo

AU - Irvine, Derek J.

AU - Stockman, Robert A.

AU - De Focatiis, Davide S.A.

AU - Howdle, Steven M.

N1 - © 2022 Published by Elsevier Ltd. Funding Information: This work was carried out with the support of Diamond Light Source, beamline I22 (proposal SM23501). Professor Nick J. Terrill and Dr Andrew J. Smith are thanked for help and advice during SAXS data collection. Funding Information: This work was supported by the Engineering and Physical Sciences Research Council [grant numbers EP/N019784/1,]; the School of Chemistry, University of Nottingham. We thank Mark Guyler (University of Nottingham) for his technical support with all the laboratory equipment. We are indebted to Shazad Aslam and Kevin Butler for their technical input to analysis by NMR. This work was carried out with the support of Diamond Light Source, beamline I22 (proposal SM23501). Professor Nick J. Terrill and Dr Andrew J. Smith are thanked for help and advice during SAXS data collection. Funding Information: This work was supported by the Engineering and Physical Sciences Research Council [grant numbers EP/N019784/1,]; the School of Chemistry, University of Nottingham. We thank Mark Guyler (University of Nottingham) for his technical support with all the laboratory equipment. We are indebted to Shazad Aslam and Kevin Butler for their technical input to analysis by NMR. Publisher Copyright: © 2022

PY - 2022/10/5

Y1 - 2022/10/5

N2 - We report the synthesis of novel terpene-based monomers: nopinyl acrylate and methacrylate, from naturally abundant β-pinene. A very high Tg value was observed for poly(nopinyl methacrylate) when synthesised by free radical polymerisation, and well-defined polymers have been produced via RAFT polymerisation. This exciting new high Tg material shows promise as a hard block in thermoplastic elastomers. ABA triblock copolymers have been synthesised which also incorporate a low Tg renewable soft block, poly(tetrahydrogeraniol methacrylate), using a divergent, difunctional RAFT polymerisation method. Initial phase separation behaviour and adhesive properties have been investigated to highlight the potential of these copolymer materials as renewably sourced thermoplastic elastomers.

AB - We report the synthesis of novel terpene-based monomers: nopinyl acrylate and methacrylate, from naturally abundant β-pinene. A very high Tg value was observed for poly(nopinyl methacrylate) when synthesised by free radical polymerisation, and well-defined polymers have been produced via RAFT polymerisation. This exciting new high Tg material shows promise as a hard block in thermoplastic elastomers. ABA triblock copolymers have been synthesised which also incorporate a low Tg renewable soft block, poly(tetrahydrogeraniol methacrylate), using a divergent, difunctional RAFT polymerisation method. Initial phase separation behaviour and adhesive properties have been investigated to highlight the potential of these copolymer materials as renewably sourced thermoplastic elastomers.

KW - Terpenes

KW - Nopinyl

KW - ABA Triblocks

KW - Biorenewable monomers

KW - RAFT

UR - https://www.sciencedirect.com/science/article/pii/S0014305722005717

UR - http://www.scopus.com/inward/record.url?scp=85138050525&partnerID=8YFLogxK

U2 - 10.1016/j.eurpolymj.2022.111567

DO - 10.1016/j.eurpolymj.2022.111567

M3 - Article

SN - 0014-3057

VL - 179

JO - European Polymer Journal

JF - European Polymer Journal

M1 - 111567

ER -

Sustainable ABA Triblock Methacrylate Copolymers Incorporating both High and Low Tg Terpene-Derived Monomers

Abstract

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Keywords

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